WO2018043165A1 - 含フッ素重合体、その製造方法、および含フッ素重合体の硬化物を備える物品 - Google Patents
含フッ素重合体、その製造方法、および含フッ素重合体の硬化物を備える物品 Download PDFInfo
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Definitions
- the present invention relates to a fluoropolymer, a production method thereof, and an article provided with a cured product of the fluoropolymer.
- Fluoropolymers are used as various industrial materials because they have excellent properties such as heat resistance, chemical resistance, low surface energy, low refractive index, and low dielectric constant.
- fluoropolymers represented by polytetrafluoroethylene (PTFE), poly (tetrafluoroethylene-hexafluoropropylene) (FEP), and poly (tetrafluoroethylene-perfluoroalkyl vinyl ether) (PFA) are related to the above properties. Has characteristic physical properties not found in other materials, whether organic or inorganic.
- Patent Document 1 proposes a liquid curable fluorinated polymer having a CF 2 ⁇ CFO— (perfluorovinyl ether) group, and a cured product having excellent heat resistance and light resistance is obtained by heat curing.
- An object of the present invention is to provide a fluorine-containing polymer that can be thermally cured at a low temperature of room temperature to 150 ° C.
- the present invention provides a fluorine-containing polymer having the following constitutions [1] to [14], a method for producing the same, and an article provided with a cured product of the fluorine-containing polymer.
- X 1 and X 2 are each independently a hydrogen atom or a fluorine atom
- Q 1 is a single bond or an etheric oxygen atom
- R f1 is a fluoroalkylene group or a fluoroalkylene group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms
- Z 1 is NR 1 -Y 1 , OY 2 or SY 3
- R 1 is a hydrogen atom, an alkyl group or an aryl group
- Y 1 , Y 2 and Y 3 are each independently a group having one or more hydrolyzable silyl groups.
- the unit represented by the formula (1) is — [CF 2 —CF (O (CF 2 ) 3 CONH—C 3 H 6 —SiR 2 m1 (W 1 ) 3-m1 )] — or — [ CF 2 —CF (O (CF 2 ) 3 CONH—C 2 H 4 —NH—C 3 H 6 —SiR 2 m1 (W 1 ) 3-m1 )] —.
- R 2 is each independently an alkyl group
- W 1 is each independently a halogen atom or an alkoxy group
- m 1 is independently 0, 1 or 2
- X 3 and X 4 are each independently a hydrogen atom, a fluorine atom or a chlorine atom
- X 5 is a hydrogen atom, a fluorine atom or a chlorine atom
- X 6 represents a hydrogen atom, a fluoroalkyl group, a fluoroalkyl group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms, a fluoroalkoxy group, or a carbon number having an etheric oxygen atom between carbon-carbon atoms.
- a production method comprising reacting a combination with at least one compound selected from the group consisting of an aminosilane compound, an epoxysilane compound, a mercaptosilane compound, and an isocyanatosilane compound.
- X 1 , X 2 , Q 1 and R f1 are as defined in claim 1
- Z 2 is as defined in claim 3.
- a coating composition comprising the fluorinated polymer according to any one of [1] to [7] and a fluorinated solvent.
- [10] A cured product of the fluoropolymer of any one of [1] to [7].
- a primer layer is provided between the surface of the base material and the cured polymer layer of the fluoropolymer.
- FIG. 1 is a graph showing the relationship between the temperature and elastic modulus of the film obtained in Example 1.
- FIG. 2 is a graph showing the relationship between the temperature and elastic modulus of the film obtained in Example 2.
- the compound represented by the formula (a) may be referred to as “compound (a)”.
- the unit represented by the formula (b) may be referred to as “unit (b)”.
- Units represented by other formulas are also described in the same manner.
- a unit derived from a monomer may be represented by adding “unit” to the monomer name.
- a unit derived from fluoroethylene is referred to as “fluoroethylene unit”.
- fluoroethylene unit The meanings of the following terms in this specification are as follows.
- Fluoroethylene means tetrafluoroethylene (CF 2 ⁇ CF 2 ), and 1 to 3 fluorine atoms of tetrafluoroethylene are a hydrogen atom or a halogen atom other than fluorine (a chlorine atom, a bromine atom or an iodine atom) It means a substituted compound.
- tetrafluoroethylene is also referred to as “TFE”
- trifluoroethylene is also referred to as “TrFE”
- chlorotrifluoroethylene is also referred to as “CTFE”.
- the fluoropolymer of the present invention contains a unit (1).
- X 1 and X 2 are each independently a hydrogen atom or a fluorine atom
- Q 1 is a single bond or an etheric oxygen atom
- R f1 is a fluoroalkylene group or a fluoroalkylene group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms
- Z 1 is NR 1 -Y 1 , OY 2 or SY 3
- R 1 is a hydrogen atom, an alkyl group or an aryl group
- Y 1 , Y 2 and Y 3 are each independently a group having one or more hydrolyzable silyl groups.
- the fluorine-containing polymer of the present invention contains a group having a hydrolyzable silyl group, it is crosslinked by hydrolysis / condensation reaction with moisture in the air to obtain a cured product.
- X 1 and X 2 are the same and are preferably fluorine atoms.
- Q 1 is preferably an etheric oxygen atom.
- R f1 is a fluoroalkylene group
- the carbon number thereof is preferably 1-6, and particularly preferably 1-4.
- the number of carbon atoms is 3 or more, a linear structure is preferable from the viewpoint of excellent thermal stability.
- a perfluoroalkylene group is preferable from the viewpoint of excellent thermal stability. That is, R f1 is preferably a perfluoroalkylene group having 1 to 6 carbon atoms, and particularly preferably a perfluoroalkylene group having 1 to 4 carbon atoms.
- R f1 is a fluoroalkylene group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms
- the carbon number thereof is preferably 2 to 10, particularly preferably 2 to 6.
- the number of carbon atoms is 3 or more, a linear structure is preferable from the viewpoint of excellent thermal stability.
- the fluoroalkylene group a perfluoroalkylene group is preferable from the viewpoint of excellent thermal stability. That is, R f1 is preferably a C 2-10 fluoroalkylene group having an etheric oxygen atom between carbon-carbon atoms, and a C 2-6 fluoro having an etheric oxygen atom between carbon-carbon atoms.
- An alkylene group is particularly preferred.
- the hydrolyzable silyl group contained in Z 1 is represented by —SiR 2 m1 (W 1 ) 3-m1 (wherein R 2 is independently an alkyl group, and W 1 is Independently, it is a halogen atom or an alkoxy group, and m1 is 0, 1 or 2.)
- R 2 preferably has 1 to 6 carbon atoms, particularly preferably 1 or 2.
- W 1 that is a halogen atom include a fluorine atom, a chlorine atom, a chlorine atom, and a bromine atom, and a fluorine atom and a chlorine atom are preferable.
- W 1 which is an alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 or 2 carbon atoms, and particularly preferably an alkoxy group having 1 carbon atom from the viewpoint of better low-temperature curability.
- the hydrolyzable silyl group is more preferably —SiCH 3 (OCH 3 ) 2 and —SiCH 3 (OC 2 H 5 ) 2 , and —SiCH 3 (OCH 3 ) 2 is preferred from the viewpoint of excellent low-temperature curability and storage stability. Particularly preferred.
- the number of hydrolyzable silyl groups in Z 1 is not particularly limited, but 1 is preferable.
- R 1 is an alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 or 2 carbon atoms is particularly preferable.
- R 1 is an aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and a phenyl group is particularly preferable.
- R 1 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and a phenyl group because it is excellent in solubility in a fluorine-containing solvent described later, and has high hydrogen bonding properties and excellent adhesion to various substrates. From the viewpoint, a hydrogen atom is particularly preferable.
- Y 1 include the following formula (10a).
- R 3 is an alkylene group, an arylene group, or an alkylene group having 2 or more carbon atoms having an amino group between carbon-carbon atoms
- R 2 , W 1 and m1 are as defined for Z 1 and the preferred ranges are also the same.
- R 3 is an alkylene group
- an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 or 3 carbon atoms is particularly preferable.
- R 3 is an arylene group
- an arylene group having 6 to 20 carbon atoms is preferable, and a phenylene group is particularly preferable.
- R 3 is an alkylene group having 2 or more carbon atoms having an amino group between carbon and carbon atoms, the number of carbon atoms is preferably 2 to 12, and more preferably 4 to 6.
- the amino group contained in R 3 is represented by —NR 4 —, wherein R 4 has the same meaning as R 1 and the preferred range is also the same.
- R 3 has 2 to 12 carbon atoms having an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 20 carbon atoms, and an amino group between carbon-carbon atoms from the viewpoint of excellent solubility in a fluorine-containing solvent.
- An alkylene group is preferably selected as appropriate, and —C 2 H 4 —, —C 3 H 6 —, a phenylene group, and an alkylene group having 4 or 5 carbon atoms having —NH— between carbon-carbon atoms are particularly preferable.
- Y 1 represents C 2 H 4 —SiR 2 m1 (W 1 ) 3-m1 , C 3 H 6 —SiR 2 m1 (W 1 ) 3-m1 and C 2 H 4 —NH—C 3 H 6 — R 2 m1 (W 1 ) 3-m1 is preferred, C 3 H 6 —SiCH 3 (OCH 3 ) 2 , C 2 H 4 —NR 4 —C 3 H 6 —Si (OC 2 H 5 ) 3 and C 2 H 4 —NR 4 —C 3 H 6 —SiCH 3 (OCH 3 ) 2 is particularly preferred.
- NR 1 -Y 1 is NHC 3 H 6 Si (OC 2 H 5 ) 3 , NHC 3 H 6 SiCH 3 (OCH) because it has excellent solubility in fluorine-containing solvents, curing reactivity, and / or storage stability.
- 3 ) 2 , NHC 2 H 4 —NH—C 3 H 6 —Si (OC 2 H 5 ) 3 and NHC 2 H 4 —NH—C 3 H 6 —SiCH 3 (OCH 3 ) 2 are preferred, NHC 3 H 6 SiCH 3 (OCH 3 ) 2 and C 2 H 4 —NH—C 3 H 6 —SiCH 3 (OCH 3 ) 2 are particularly preferred.
- Y 2 examples include the following formula (10b).
- R 5 is an alkylene group, an alkylene group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms, an etheric oxygen atom between carbon-carbon atoms, and one or more hydrogen atoms substituted with hydroxyl groups
- An alkylene group having 2 or more carbon atoms and an arylene group, R 2 , W 1 and m1 are as defined for Z 1 and the preferred ranges are also the same.
- R 5 is an alkylene group
- the carbon number thereof is preferably 1 to 6, and particularly preferably 1 or 2.
- the number of carbon atoms is preferably 2 to 12, and more preferably 3 to 6.
- the number of carbon atoms is preferably 2 to 12 3 to 8 are particularly preferred.
- R 5 is an alkylene group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms and one or more hydrogen atoms substituted with a hydroxyl group
- CH 2 CH (OH) —R The group represented by 6 is preferred.
- R 6 is an alkylene group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms.
- R 6 preferably has 2 to 10 carbon atoms and particularly preferably 3 or 4 from the viewpoint of easy synthesis.
- R 5 a synthetic easiness, carbon - preferably an alkylene group having 2 or more carbon atoms and having an etheric oxygen atom is 1 or more hydrogen atoms are replaced by hydroxyl groups between carbon atoms, CH 2 CH (OH) CH 2 OC 3 H 6 is particularly preferred.
- a specific example of Y 3 in SY 3 includes formula (10a).
- Z 1 include the following groups. —NHC 3 H 6 Si (OCH 3 ) 3 —NHC 3 H 6 Si (OC 2 H 5 ) 3 —NHC 3 H 6 SiCH 3 (OCH 3 ) 2 —NHC 3 H 6 SiCH 3 (OC 2 H 5 ) 2 —NHC 2 H 4 NHC 3 H 6 Si (OCH 3 ) 3 —NHC 2 H 4 NHC 3 H 6 Si (OC 2 H 5 ) 3 —NHC 2 H 4 NHC 3 H 6 Si (OC 2 H 5 ) 3 —NHC 2 H 4 NHC 3 H 6 SiCH 3 (OCH 3 ) 2 —NHC 2 H 4 SiCH 3 (OC 2 H 5 ) 2 -N (C 6 H 5) C 3 H 6 Si (OCH 3) 3 —N (C 6 H 5 ) C 3 H 6 Si (OC 2 H 5 ) 3 -N (C 6 H 5) C 3 H 6 SiCH 3 (OCH 3) 2 -N (C 6 H 5 ) C 3 H 6
- the unit (1) include the following units. — [CF 2 —CF (O (CF 2 ) 2 —COZ 1 )] — — [CF 2 —CF (O (CF 2 ) 3 —COZ 1 )] — — [CF 2 —CF (O (CF 2 ) 4 —COZ 1 )] — — [CF 2 —CF (OCF 2 CF (CF 3 ) O (CF 2 ) 2 —COZ 1 )] — — [CF 2 —CF (OCF 2 CF (CF 3 ) O (CF 2 ) 3 —COZ 1 )] — — [CF 2 —CF (O (CF 2 ) 3 O (CF 2 ) 2 —COZ 1 )] — — [CF 2 —CF (O (CF 2 ) 3 O (CF 2 ) 2 —COZ 1 )] — — [CF 2 —CF (O (CF 2 ) 3 O (CF 2 ) 2 —COZ 1 )
- the fluoropolymer of the present invention may contain units other than the unit (1).
- Other units include a unit (1a) described later, a unit (1b) described later, a fluoroethylene unit (hereinafter also referred to as “unit (2)”), a unit (3) described later, and a unit (1).
- Units (1a), units (1b), units (2), and units other than unit (3) hereinafter also referred to as “unit (4)”.
- the fluoropolymer of the present invention preferably contains the unit (1a) from the viewpoint that UV curing is possible.
- Z 1 in the unit (1) is NR 1 -Y 1 and Z 2 is OR 7 from the viewpoint that heat curing and UV curing can be used in combination.
- a unit (1b) is included from the point which improves the adhesiveness to various base materials.
- Other units can be used alone or in combination of two or more.
- the fluoropolymer may contain a single unit (1b) and two or more types of units (2).
- the unit (1a) is a unit represented by the following formula (1a).
- X 1 , X 2 , Q 1 and R f1 are as defined in formula (1), Z 2 is a halogen atom, OH or OR 7 ; R 7 is an alkyl group.
- Z 2 is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a fluorine atom or a chlorine atom is preferable.
- R 7 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably —CH 3 and —C 2 H 5, and particularly preferably —CH 3 .
- Z 2 is preferably OR 7 from the viewpoint that when the unit (1) is formed by reaction with an aminosilane compound described later, gelation does not occur and the reaction can be performed stably.
- Unit (1a) can be formed by polymerizing compound (11) as a monomer.
- CX 1 X 2 CF-Q 1 -R f1 -COZ 2 (11)
- X 1 , X 2 , Q 1 and R f1 are as defined in formula (1)
- Z 2 is as defined in formula (1a).
- the unit (1b) is a unit represented by the following formula (1b).
- Z 3 is NR 8 H or NR 9 -NR 10 H;
- R 8 and R 9 are each independently a hydrogen atom or an alkyl group,
- R 10 is a hydrogen atom or a methyl group,
- X 1 , X 2 , Q 1 and R f1 are as defined in formula (1).
- the unit (1b) is a fluorine-containing polymer containing a unit (1a) in which Z 2 is OR 7 , and an amine compound represented by the following formula (12) (hereinafter also referred to as “amine compound (12)”). And at least one compound selected from the group consisting of a hydrazine compound represented by the following formula (13) (hereinafter also referred to as “hydrazine compound (13)”).
- amine compound (12) an amine compound represented by the following formula (12)
- hydrazine compound (13) at least one compound selected from the group consisting of a hydrazine compound represented by the following formula (13) (hereinafter also referred to as “hydrazine compound (13)”).
- Examples of the amine compound (12) include ammonia, methylamine, ethylamine, propylamine, isopropylamine and the like.
- Examples of the hydrazine compound (13) include hydrazine, phenyl hydrazine, methyl hydrazine, 1,2-dimethylhydrazine and the like.
- the total amount of the amine compound (12) and hydrazine compound (13) used in the reaction is 1 mol of the group represented by —COOR 7 of the fluoropolymer containing the unit (1a) in which Z 2 is OR 7.
- it is not particularly limited as long as a fluoropolymer having the desired amount of —COZ 3 is obtained, but it is preferably 0.1 to 20 mol, more preferably 0.3 to 15 mol, and more preferably 0.5 to 10 mol. Is particularly preferred.
- the reaction can be carried out in the presence of a solvent.
- the solvent can preferably dissolve the raw material component (the fluoropolymer containing the unit (1a) in which Z 2 is OR 7 , the amine compound (12), and the hydrazine compound (13)), but at least Z 2 is OR 7 It is preferable to use a solvent in which the fluoropolymer containing a certain unit (1a) is dissolved.
- a solvent the fluorine-containing solvent mentioned later is mentioned.
- a fluorine-containing polymer containing the unit (1a) in which Z 2 is OR 7 is dissolved in the above-mentioned fluorine-containing solvent, and the amine compound (12) and the hydrazine compound (13) are formed at 0 to 30 ° C. It is carried out by adding one or more compounds selected from the group. After the addition, the fluorine-containing polymer having the unit (1b) can be obtained by heating to 30 to 100 ° C. and reacting for 1 minute to 10 hours.
- Unit (2) is a fluoroethylene unit.
- the unit (2) include a TFE unit, a TrFE unit, a CTFE unit, and a vinylidene fluoride unit. From the viewpoint of excellent heat resistance, TFE units, TrFE units and CTFE units are preferred. From the point that the fluorine-containing polymer and the cured product of the fluorine-containing polymer are excellent in adhesiveness to the base material since the highly polar —COZ 1 group tends to exist at the interface while maintaining the chemical resistance. Units are particularly preferred. TrFE units and CTFE units are particularly preferred because they are highly soluble and the fluoropolymer and the cured product of the fluoropolymer are excellent in adhesiveness regardless of the content of -COZ 1 group.
- the unit (3) is a unit represented by the following formula (3) (excluding the fluoroethylene unit). -[CX 3 X 4 -CX 5 X 6 ] -... (3)
- X 3 and X 4 are each independently a hydrogen atom, a fluorine atom or a chlorine atom
- X 5 is a hydrogen atom, a fluorine atom or a chlorine atom
- X 6 represents a hydrogen atom, a fluoroalkyl group, a fluoroalkyl group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms, a fluoroalkoxy group, or a carbon number having an etheric oxygen atom between carbon-carbon atoms.
- It is a fluoroalkenyl group having 3 or more carbon atoms having an etheric oxygen atom between two or more fluoroalkoxy groups, fluoroalkenyl groups, or carbon-carbon atoms.
- X 6 is a fluoroalkyl group
- the carbon number thereof is preferably 1 to 15, and particularly preferably 1 to 6.
- a perfluoroalkyl group is preferred, a C 1-6 perfluoroalkyl group is more preferred, and —CF 3 is particularly preferred.
- the carbon number is preferably 2 to 15 and particularly preferably 2 to 6.
- a perfluoroalkyl group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms is preferable, and perfluorocarbon having an etheric oxygen atom between carbon-carbon atoms is preferred.
- Alkyl groups are particularly preferred.
- X 6 is a fluoroalkoxy group
- the carbon number thereof is preferably 1 to 15, and more preferably 1 to 6.
- a perfluoroalkoxy group having 1 to 6 carbon atoms is preferable, and —OCF 3 , —OCF 2 CF 3 , —O (CF 2 ) 2 CF 3 , —OCF 2 CF (CF 3 ) O (CF 2 ) 2 CF 3 is particularly preferred.
- X 6 is a fluoroalkoxy group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms
- the carbon number thereof is preferably 2 to 15, and particularly preferably 2 to 6.
- a perfluoroalkoxy group having 2 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms is preferred, and a perfluorocarbon having 2 to 6 carbon atoms having an etheric oxygen atom between carbon-carbon atoms.
- Alkoxy groups are particularly preferred.
- the fluoroalkoxy group having an etheric oxygen atom —OCF 2 CF (CF 3 ) O (CF 2 ) 2 CF 3 is most preferable.
- the number of carbon atoms is preferably 5 to 15 because the cyclization reaction does not proceed in the molecule and the synthesis is easy. From the viewpoint of excellent thermal stability, a perfluoroalkenyl group is preferable, and — (CF 2 ) 4 CF ⁇ CF 2 , — (CF 2 ) 5 CF ⁇ CF 2 and — (CF 2 ) 6 CF ⁇ CF 2 are Particularly preferred.
- Y 2 is a fluoroalkenyl group having 3 or more carbon atoms having an etheric oxygen atom between carbon-carbon atoms, the number of carbon atoms is preferably 3 to 16, and more preferably 3 to 7.
- a perfluoroalkenyl group having 3 or more carbon atoms having an etheric oxygen atom between carbon and carbon atoms is preferred, and a perfluoro having 3 to 7 carbon atoms having an etheric oxygen atom between carbon and carbon atoms.
- Alkenyl groups are particularly preferred.
- the glass transition temperature of the fluorine-containing polymer is lowered, the fluidity is excellent, and the moldability is excellent. Also, when the fluorine-containing polymer is cured by at least one of heating and active energy ray irradiation, the molecule has high mobility.
- the unit (3) has — [CH 2 —CH 2 ] —, — [CF 2 —CF (CF 3 )] —, — [CF 2 —CF (OCF 3 ) ]-,-[CF 2 -CF (O (CF 2 ) 2 CF 3 )]-and-[CF 2 -CF (OCF 2 CF (CF 3 ) O (CF 2 ) 2 CF 3 )]-are preferred.
- Unit (3) can be formed by polymerizing compound (31) as a monomer.
- CX 3 X 4 CX 5 X 6 (31)
- X 3 , X 4 , X 5 and X 6 are as defined in formula (3).
- X 6 is the fluoroalkenyl group
- the double bond in the fluoroalkenyl group in the compound (31) does not participate in the polymerization, and the unit (3) having a fluoroalkenyl group is obtained by the polymerization of the compound (31). It is formed.
- the content of the group represented by —COZ 1 in the fluoropolymer of the present invention is preferably 0.01 to 4 mmol / g, and preferably 0.01 to 2 mmol / g with respect to the mass of the fluoropolymer. More preferably, 0.04 to 2 mmol / g is more preferable, and 0.1 to 1 mmol / g is particularly preferable.
- the content of the group represented by —COZ 1 is a total ratio of CO—NR 1 —Y 1 , CO—O—Y 2 and CO—S—Y 3 .
- the fluoropolymer When it is at least the lower limit of the above range, the fluoropolymer is crosslinked, and the resulting fluoropolymer cured product is excellent in mechanical strength and thermal stability. When it is at most the upper limit of the above range, the cured product of the fluoropolymer is excellent in solvent resistance and chemical resistance.
- a group Z 1 is represented by -COZ 1 is NR 1 -Y 1
- Z 1 is represented by -COZ 1 is O-Y 2
- Z the content of each of groups 1 is represented by -COZ 1 is S-Y 3, relative to the mass of the fluoropolymer, preferably 0.01 ⁇ 2mmol / g, 0.02 ⁇ 1mmol / g Is more preferable, and 0.05 to 0.5 mmol / g is particularly preferable.
- it is at least the lower limit of the above range, a crosslinked structure of siloxane is formed, and even when exposed to a solvent, the cured product of the fluoropolymer is not easily dissolved or cracked.
- the amount is not more than the upper limit of the above range, the coating composition containing a fluoropolymer described later is difficult to gel and excellent in storage stability.
- the fluoropolymer of the present invention contains at least one of the unit (1a) and the unit (1b), the total content of groups represented by —COZ 1 , —COZ 2 and —COZ 3 is 0.01 to 4 mmol / g is preferable, 0.01 to 2 mmol / g is more preferable, 0.04 to 2 mmol / g is more preferable, and 0.1 to 1 mmol / g is particularly preferable with respect to the mass of the polymer. .
- the fluoropolymer is crosslinked, and the resulting fluoropolymer cured product is excellent in mechanical strength and thermal stability.
- the cured product of the fluoropolymer is excellent in solvent resistance and chemical resistance.
- the ratio of the groups represented by —COZ 1 , —COZ 2 and —COZ 3 in the unit (1) in the fluoropolymer can be calculated by 19 F-NMR measurement.
- the content of the unit (1) in all the units of the fluoropolymer is preferably 0.1 to 100 mol%, more preferably 0.5 to 50 mol%, further preferably 1 to 10 mol%, particularly 2 to 5 mol%. preferable.
- it is at least the lower limit of the above range a crosslinked structure of siloxane is formed, and even when exposed to a solvent, the cured product of the fluoropolymer is not easily dissolved or cracked.
- the amount is not more than the upper limit of the above range, the coating composition containing a fluoropolymer described later is difficult to gel and excellent in storage stability.
- a preferred embodiment of the fluoropolymer is a fluoropolymer containing the unit (1), the unit (1a), the unit (2) and the unit (3), wherein the unit (1 ) Is 0.1 to 99.7 mol%, the proportion of units (1a) is 0.1 to 98 mol%, the proportion of units (2) is 0.1 to 80 mol%, Fluoropolymer having a ratio of 3) of 0.1 to 98 mol%, and also a fluoropolymer comprising units (1), units (1a), units (1b), units (2) and units (3) Wherein the content of the unit (1) is 0.1 to 99.6 mol% and the proportion of the unit (1a) is 0.1 to 98 mol% in all the units of the fluoropolymer, 1b) is 0.1 to 98 mol%, and the unit (2) is 0.1 to 80 mol%. The proportion of the unit (3) is 0.1 ⁇ 95 mol%.
- the content of each unit in the fluoropolymer can be calculated by 19 F-N
- the mass average molecular weight of the fluoropolymer of the present invention is preferably from 5,000 to 500,000, particularly preferably from 10,000 to 100,000.
- the cured product of the fluoropolymer is excellent in mechanical strength, and when it is at most the upper limit of the above range, the viscosity when dissolved in the fluorine-containing solvent is from 1 to 100 Pa ⁇ s.
- the thickness of the cured product of the fluoropolymer is easy to adjust.
- the mass average molecular weight can be determined as a PMMA (polymethyl methacrylate) equivalent molecular weight by gel permeation chromatography (GPC). Moreover, it can also estimate from the molecular weight of the precursor mentioned later.
- PMMA polymethyl methacrylate
- GPC gel permeation chromatography
- the fluorine-containing polymer of the present invention comprises a fluorine-containing polymer containing the unit (1a) and not containing the unit (1) (hereinafter also simply referred to as “precursor”), an aminosilane compound, an epoxysilane compound, and a mercapto. It can be produced by reacting with at least one silane compound selected from the group consisting of silane compounds and isocyanatosilane compounds. These silane compounds can be used alone or in combination of two or more.
- the precursor further comprises the above unit (1b), unit (2), unit (3) and unit (4) in addition to unit (1a). Having at least one unit selected from the group.
- the precursor is obtained by polymerizing by a known method (for example, a method described in International Publication No. 2015/098773).
- aminosilane compound a compound represented by the following formula (5) is preferable.
- HNR 1 -Y 1 (5) R 1 and Y 1 are as defined in formula (1), and the preferred ranges are also the same.
- aminosilane compounds include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3- Aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3- Aminopropylmethyldiethoxysilane, N-phenyl-3-amino
- Ep-Y 21 (6) a compound represented by the following formula (6) is preferable.
- Ep is an epoxy group (that is, 1,2-epoxyethyl group)
- Y 21 is synonymous with Y 2
- R 6 —SiR 2 m1 (W 1 ) 3-m1 is preferable.
- the epoxysilane compound 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane are particularly preferable.
- mercaptosilane compound a compound represented by the following formula (7) is preferable.
- HS-Y 3 (7) Y 3 is as defined in formula (1), and the preferred range is also the same.
- mercaptosilane compound 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, and 3-mercaptopropyltriethoxysilane are particularly preferable.
- isocyanatosilane compound a compound represented by the following formula (8) is preferable.
- Y 4 has the same meaning as Y 3 , and the preferred range is also the same.
- isocyanatosilane compound 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, and 3-isocyanatopropyltriethoxysilane are preferable.
- the fluoropolymer contains a unit in which Z 1 is NR 1 -Y 1
- it can be produced by the following method.
- A a precursor containing a unit (1a) in which Z 2 is OR 7 and an aminosilane compound
- b a precursor containing a unit (1a) in which Z 2 is a halogen atom, and an aminosilane compound or isocyanate
- C reacting with a natosilane compound
- c reacting a precursor containing a unit (1a) in which Z 2 is OH with an isocyanatosilane compound
- the fluoropolymer contains a unit in which Z 1 is OY 2 , it can be produced by the following method.
- the fluorine-containing polymer contains a unit in which Z 1 is SY 3 , it can be produced by the following method.
- the total reaction amount of the silane compound is not particularly limited as long as a fluoropolymer having a desired amount of —COZ 1 is obtained with respect to 1 mol of the group represented by —COZ 2 in the precursor. 0.1 to 10 mol is preferable, 0.3 to 5 mol is more preferable, and 0.5 to 2 mol is particularly preferable.
- the reaction can be performed in the absence or presence of a solvent.
- the solvent can dissolve the raw material components (precursor and the silane compound), and it is particularly preferable to use a solvent in which at least the precursor is dissolved. In this case, the reaction is performed in a state where the raw material components are dissolved or dispersed in the solvent.
- a solvent is a fluorine-containing solvent.
- fluorinated solvent examples include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
- fluorinated alkane a compound having 4 to 8 carbon atoms is preferable.
- Commercially available products include, for example, C 6 F 13 H (Asahi Glass Co., Ltd., Asahi Culin (registered trademark) AC-2000), C 6 F 13 C 2 H 5 (Asahi Glass Co., Ltd., Asahi Clin (registered trademark) AC-6000).
- C 2 F 5 CHFCHFCF 3 (manufactured by Chemers, Bertrell (registered trademark) XF), and the like.
- fluorinated aromatic compound examples include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis (trifluoromethyl) benzene.
- fluoroalkyl ether a compound having 4 to 12 carbon atoms is preferable.
- Examples of commercially available products include CF 3 CH 2 OCF 2 CF 2 H (Asahi Glass Co., Ltd., Asahi Clin (registered trademark) AE-3000), C 4 F 9 OCH 3 (manufactured by 3M, Novec (registered trademark) 7100), C 4 F 9 OC 2 H 5 (manufactured by 3M, Novec (registered trademark) 7200), C 2 F 5 CF (OCH 3 ) C 3 F 7 (manufactured by 3M, Novec (registered trademark) 7300), etc. .
- Examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
- Examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.
- the fluorine-containing solvent preferably has a fluorine atom content of 60% or more, more preferably 65 to 77%, and particularly preferably 70 to 77% from the viewpoint of excellent solubility of the fluorine-containing polymer.
- a fluorine-containing solvent containing a hydrogen atom is preferable from the viewpoint of excellent dispersibility of the fluorine-containing polymer.
- a fluorine-containing solvent can be used individually or in combination of 2 or more types.
- the solvent is a fluorinated solvent
- another solvent may be used in combination.
- Other solvents include ether compounds and alcohol compounds.
- Other solvents can be used to dissolve and dilute the silane compound.
- Other solvents can be used alone or in combination of two or more.
- the amount of the solvent used is preferably 50 to 99 parts by mass, particularly preferably 70 to 95 parts by mass with respect to 100 parts by mass in total of the precursor and the silane compound. .
- the reaction is preferably performed by, for example, dissolving the precursor in the above solvent and then adding the silane compound at 0 to 30 ° C.
- the target fluoropolymer can be obtained by heating to 30 to 100 ° C. and reacting for 1 minute to 10 hours.
- the fluoropolymer of the present invention is crosslinked by hydrolysis / condensation reaction with moisture to obtain a cured product. Therefore, the fluoropolymer of the present invention can be molded and cured with moisture to produce a molded product.
- the fluoropolymer of the present invention is usually a liquid with a high viscosity, and the molding requires molding using a liquid. Therefore, it is preferable to produce a cured product by forming a fluoropolymer film on a carrier, bringing the surface of the film into contact with moisture, and allowing the moisture to penetrate into the film and curing.
- a molded body made of the cured product By exfoliating the cured product from the carrier, a molded body made of the cured product can be obtained.
- a non-peelable carrier can be used as the carrier, and a molded body in which the cured product is integrated on the carrier can be obtained.
- the non-peelable carrier is referred to as “substrate”.
- Moisture is required for the curing of the fluoropolymer, and the supply of moisture is usually performed by bringing the moisture-containing air into contact with the fluoropolymer film.
- the supply of moisture can also be performed by contacting with a gas other than air containing moisture or by contacting with a water-containing liquid.
- the molded body obtained by using a peelable carrier and separating from the peelable carrier is preferably a thin planar body having a shape such as a film shape or a sheet shape.
- a planar body is referred to as a “film”.
- the thickness of the film is preferably 1 to 500 ⁇ m, more preferably 10 to 400 ⁇ m, and particularly preferably 30 to 300 ⁇ m.
- the fluoropolymer is sufficiently cured, and a film having good physical properties can be obtained. Above the lower limit of the thickness, the film can be separated from the peelable carrier and used as a single film.
- the releasable carrier include a carrier made of a non-adhesive material such as a fluororesin, and a carrier made of various materials such as a resin and a metal having a peelable surface by surface treatment.
- a carrier having at least a surface made of a non-adhesive fluorine-containing material is preferable.
- the shape of the substrate is not particularly limited, and examples thereof include a plate shape, a rod shape, a tubular shape, a string shape, and a fiber shape.
- the material for the substrate include metals, glass, ceramics, resins, rubbers, and the like.
- the metal include iron and iron alloys, aluminum and aluminum alloys, copper and copper alloys, nickel and nickel alloys, and the like.
- the resin include acrylic resin, vinyl chloride resin, thermoplastic polyester resin, polycarbonate resin, and silicone resin.
- the surface of the substrate may have a primer layer. The primer that forms the primer layer is appropriately selected depending on the combination of the substrate and the solvent in the coating composition described later.
- a silane coupling agent or an epoxy elastomer can be used.
- the primer layer is preferably provided on a substrate that may have insufficient adhesion between the substrate surface and the cured product layer.
- a substrate include a substrate having a resin surface.
- the resin surface may be treated by UV treatment, corona treatment, plasma treatment or the like. You may have a primer layer on the surface of resin which processed these.
- the thickness of the cured product can be made thinner than the thickness of the film.
- the cured product integrated with the base material is referred to as a “layer” on the base material.
- the thickness of the layer is preferably from 0.1 to 300 ⁇ m, more preferably from 1 to 200 ⁇ m, particularly preferably from 10 to 150 ⁇ m. Below the upper limit of the thickness, the fluoropolymer is sufficiently cured and a cured product integrated with the substrate is obtained. Above the lower limit, the strength of the cured product is secured and the function of protecting the substrate is exhibited.
- a composition containing the fluoropolymer of the present invention and a solvent (hereinafter referred to as “coating”) is used to form a fluoropolymer film. It is preferable to use a "composition”.
- a film of a fluoropolymer can be formed by applying the coating composition to a peelable carrier or a substrate and removing the solvent. At this time, since the liquid film can be formed using a liquid having a viscosity lower than that of the fluoropolymer, the coating operation is easy, and the thickness of the fluoropolymer film can be easily adjusted. It is.
- the coating composition and the method of using the coating composition will be described by taking as an example the case of forming a layer comprising a cured product of the fluoropolymer of the present invention on a substrate.
- films and other molded products can be produced by the following coating composition and its method of use.
- the coating composition in the present invention contains the fluoropolymer of the present invention and a solvent. You may use the reaction product containing the fluoropolymer at the time of manufacturing a fluoropolymer and a fluorine-containing solvent as it is.
- the content of the fluoropolymer in the coating composition is preferably 1 to 99% by mass, more preferably 1 to 50% by mass, and particularly preferably 5 to 30% by mass. Within this range, the thickness of the cured product of the fluoropolymer can be adjusted.
- the aforementioned fluorine-containing solvent is preferable.
- the aforementioned ether compound or alcohol compound may be used in combination with the aforementioned fluorine-containing solvent.
- the content of the solvent in the coating composition is preferably 1 to 99% by mass, more preferably 50 to 99% by mass, and particularly preferably 70 to 95% by mass.
- the content of the fluorinated solvent in the solvent is preferably 50 to 100% by mass, particularly preferably 80 to 100% by mass.
- a coating composition can be apply
- the coating composition may contain other components such as a curing catalyst, inorganic particles, alkoxysilane, a silane coupling agent, and a fluoropolyether compound as necessary.
- the other components can be used alone or in combination of two or more.
- Curing catalysts include tetraisopropyl titanate, tetrabutyl titanate, titanium acetylacetonate, aluminum triisobutoxide, aluminum triisopropoxide, tris (acetylacetonato) aluminum, diisopropoxy (ethylacetoacetate) aluminum, dibutyltin dilaurate, Examples thereof include organic metal compounds such as dibutyltin dioctylate, and organic acids having a larger acid dissociation constant than acetic acid in a nonaqueous solvent system.
- the organic acid examples include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, oxalic acid, trichloroacetic acid, trifluoroacetic acid, pentafluorobenzoic acid, hexafluoroglutaric acid, octafluoroadipic acid, and the like.
- p-toluenesulfonic acid is preferable in that it can promote condensation.
- the content of the curing catalyst in the coating composition is preferably from 0.01 to 1% by mass, particularly preferably from 0.05 to 0.2% by mass, based on the fluoropolymer. Within the above range, the curing rate is excellent and the storage stability of the coating composition is excellent.
- inorganic particles include metal oxides such as silica, titania, zirconia, and alumina, and various phosphor particles.
- the diameter of the inorganic particles is not particularly limited, but is preferably 1 to 100 nm, and particularly preferably 1 to 20 nm. Within the above range, light scattering of the cured product of the fluoropolymer can be suppressed.
- the content of the inorganic particles in the coating composition is preferably 20 to 200% by mass, particularly preferably 50 to 100% by mass with respect to the fluoropolymer. It is excellent in the refractive index of the hardened
- a coating composition is excellent in applicability
- the adhesion of the cured product of the fluoropolymer to the substrate is excellent.
- Tg glass transition temperature
- the viscosity is lowered, so that the amount of the solvent can be reduced.
- the silane coupling agent and the fluoropolyether compound include those described in International Publication No. 2015/0987773.
- the alkoxysilane include those described in the Shin-Etsu Chemical catalog or the Momentive Performance Materials catalog.
- the total content of other components in the coating composition is preferably 1 to 70% by mass, particularly preferably 5 to 50% by mass.
- the solid content of the coating composition is preferably 1 to 99% by mass.
- the cured product of the fluoropolymer of the present invention can be produced by a method comprising applying the coating composition of the present invention to the surface of a substrate, then removing the solvent and curing by heating. Since the fluoropolymer of the present invention has a hydrolyzable silyl group, it is crosslinked at a low temperature with moisture in the air. Crosslinking occurs in the process of solvent removal or heating after solvent removal. It is preferable to perform the solvent removal and the heating after the solvent removal at a low temperature. Low temperature means that the temperature is in the range of room temperature (for example, 20 ° C.) to 150 ° C., preferably from room temperature to less than 100 ° C., particularly preferably in the range of room temperature to 90 ° C.
- the material of the substrate is metal or ceramic
- the material of the substrate is resin
- the coating composition can be applied by spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, ink jet, flow coating, roll coating, casting, Langmuir / Blodget Method, gravure coating method and the like.
- Curing of the fluoropolymer of the present invention can also be performed using ultraviolet rays.
- Z 1 contains a unit having OR 7
- a crosslinking reaction occurs in the same manner as described in WO2015 / 098773.
- Examples 1 to 4 and 6 to 7 are examples, and examples 5 and 8 are comparative examples. Each example was evaluated according to the method described below.
- V601 manufactured by Wako Pure Chemical Industries, Ltd.
- the contents were transferred to a 5 L glass beaker and 4 L of methanol was added with stirring.
- 107.5 g of the precursor P1 was obtained by distilling off the remaining monomer component by heating the lower layer under reduced pressure.
- the coating composition was poured into a box-type boat (2 cm long, 2 cm wide, 7 mm deep) made of an ETFE sheet (Aflex manufactured by Asahi Glass Co., Ltd.) and heated on a hot plate at 40 ° C. for 1 hour, then at 60 ° C. for 1 hour.
- the solvent was volatilized to produce a colorless and transparent film having a thickness of 160 ⁇ m.
- Example 2 After 1.2 g of the precursor P1 obtained in Example 1 was dissolved in 6.8 g of AC-2000, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was dehydrated methanol. Then, 0.12 g of the solution diluted 5 times was added and stirred vigorously at room temperature to obtain a reaction product containing the fluoropolymer P22. A part (1.2 g) of the reaction product was used as a coating composition.
- the content of the fluorine-containing polymer P22 in the coating composition is 15.1% by mass
- the content of the solvent in the coating composition is 84.8% by mass
- the content of the fluorine-containing solvent in the solvent is It was 98.6 mass%.
- the coating composition was poured into a box-type boat similar to that of Example 1, and the solvent was evaporated by heating on a hot plate at 30 ° C., 50 ° C., and 70 ° C. for 1 hour each to prepare a film having a thickness of 230 ⁇ m.
- Example 3 After 1.2 g of the precursor P1 obtained in Example 1 was dissolved in 6.8 g of AC-2000, 0.05 g of aminopropyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added until the solution became homogeneous. The mixture was vigorously stirred at room temperature to obtain a reaction product containing a fluoropolymer P23. A part (1.2 g) of the reaction product was used as a coating composition. The content of the fluorinated polymer P23 in the coating composition is 15.2% by mass, the content of the solvent in the coating composition is 84.5% by mass, and the content of the fluorinated solvent in the solvent is It was 100% by mass.
- the coating composition was poured into a box-type boat similar to that in Example 1, and the solvent was evaporated by heating on a hot plate at 30 ° C., 50 ° C., and 70 ° C. for 1 hour each to prepare a film having a thickness of 200 ⁇ m.
- Example 4 A reaction product containing a fluoropolymer P24 was obtained in the same manner as in Example 1 except that Novec 7300 (C 2 F 5 CF (OCH 3 ) C 3 F 7 ) was used instead of AC-2000. A part (1.2 g) of the reaction product was used as a coating composition. The content of the fluorinated polymer P24 in the coating composition is 12.0% by mass, the content of the solvent in the coating composition is 87.8% by mass, and the content of the fluorinated solvent in the solvent is It was 97.8% by mass.
- the coating composition was poured into a box boat similar to Example 1, and the solvent was evaporated by heating on a hot plate at 40 ° C., 1 hour, 60 ° C., 1 hour, and then 90 ° C. for 30 minutes. A mottled film was obtained.
- the evaluation results are shown in Tables 1 and 2.
- 0.8 g of the coating composition is poured onto a box-type board similar to Example 1 and heated at 40 ° C., 1 hour, 60 ° C., 1 hour, then 90 ° C., 30 minutes, 150 ° C., 30 minutes, and 100 ⁇ m thick colorless. A transparent film was obtained.
- 1.6 g of the coating composition produced in the same manner as above was poured into a box-type board similar to Example 1, and 40 ° C, 1 hour, 60 ° C, 1 hour, then 90 ° C, 30 minutes, 150 ° C, 30 minutes. Although an attempt was made to obtain a film having a thickness of 200 ⁇ m by heating, the film was foamed and the appearance was poor.
- Example 1 a film having a thickness of 200 ⁇ m was obtained by low-temperature heating at 60 ° C. (Example 1) to 90 ° C. (Example 4), and low-temperature curing was possible. Comparing Example 1 to Example 3, Example 1 and Example 2 in which the alkoxy group of the hydrolyzable silyl group has 1 carbon have a result of “ ⁇ (good)” in the immersion test and heat resistance test. The reaction was more advanced. When Example 1 and Example 4 are compared, Example 1 in which the fluorine content of the fluorine-containing solvent contained in the coating composition is high has a high solubility of the fluorine-containing polymer, and a film having a good appearance is obtained.
- Example 5 a film could not be formed at a low temperature of 60 ° C., and low temperature curing was not possible. Further, even when the film was thermally cured by heating at 150 ° C., foaming was confirmed at the time of curing in the film having a thickness of 200 ⁇ m.
- Example 6 One part of Epofriend (manufactured by Daicel, epoxidized thermoplastic elastomer) was dissolved in 100 parts of cyclopentanone to prepare a primer solution. A primer solution was applied to one side of a hard vinyl chloride resin sheet (size 3 cm ⁇ 5 cm, thickness 1 mm) and dried at room temperature for 1 day to form a primer layer having a thickness of 10 ⁇ m. Next, the coating composition obtained in Example 2 was applied onto the primer layer and dried by heating at room temperature for 1 hour, at 50 ° C. for 1 hour, and at 70 ° C. for 5 minutes, to obtain a fluoropolymer P22 having a thickness of 60 ⁇ m. A layer of cured product was formed.
- Epofriend manufactured by Daicel, epoxidized thermoplastic elastomer
- the fluoropolymer of the present invention As a result of cross-cutting tape peeling on the cured product layer, one of the 100 places remains without being peeled off, and the cured product of the fluoropolymer of the present invention is hard vinyl chloride resin. On the other hand, it could be bonded via a primer.
- the fluoropolymer of the present invention can be cured and adhered to a resin substrate having a limited heat resistance temperature.
- Example 7 The coating composition of Example 2 was applied to one side of a nickel test piece having a size of 2 cm ⁇ 5 cm and a thickness of 2 mm, and dried at room temperature for 1 hour, at 50 ° C. for 1 hour, and then at 100 ° C. for 30 minutes. A layer of a cured product of the fluoropolymer P22 was formed. As a result of peeling the cross cut tape on the cured product layer, one part remained without being peeled off, and it was directly bonded without a primer. Thus, the fluoropolymer of the present invention can be directly cured and adhered to a metal substrate.
- Example 8 A layer of fluoropolymer X having a thickness of 50 ⁇ m was formed on a nickel test piece in the same manner as in Example 7 except that the coating composition of Example 5 was used instead of the coating composition of Example 2, and then low-pressure mercury The fluoropolymer X was cured by irradiation with ultraviolet light from a lamp. When the cross-cut tape was peeled from the cured fluoropolymer X layer, only 10 of the 100 coatings remained. Therefore, the fluorine-containing polymer of Example 5 of the known example was poor in adhesion to nickel.
- the fluoropolymer which can be thermoset at low temperature can be provided.
- the fluorine-containing polymer of the present invention is useful as an optical material, an element sealing material, an inorganic EL phosphor dispersion material, an optical waveguide material, a heat- and chemical-resistant sealing material, an adhesive, and a coating material.
- the coating composition of the present invention is useful as a mold release agent, antifouling coating material, chemical-resistant protective coating material and the like.
- a molded article made of a cured product formed from the fluoropolymer of the present invention is useful as a clad material for optical fibers, a core material for optical waveguides, and a clad material.
- a substrate provided with a cured product formed from the fluoropolymer of the present invention is useful as a light emitting element, a semiconductor element, a solar cell element, a short wavelength light emitting element, an electric wire, a coil using the same, and the like. It should be noted that the entire contents of the specification, claims, abstract and drawings of Japanese Patent Application No. 2016-167131 filed on Aug. 29, 2016 are cited here as disclosure of the specification of the present invention. Incorporated.
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Abstract
Description
[1]下式(1)で表される単位を含む、含フッ素重合体。
X1およびX2は、それぞれ独立に、水素原子またはフッ素原子であり、
Q1は、単結合またはエーテル性酸素原子であり、
Rf1は、フルオロアルキレン基、または炭素-炭素原子間にエーテル性酸素原子を有する炭素数2以上のフルオロアルキレン基であり、
Z1は、NR1-Y1、O-Y2またはS-Y3であり、
R1は、水素原子、アルキル基またはアリール基であり、
Y1、Y2およびY3は、それぞれ独立に、1以上の加水分解性シリル基を有する基である。)
[2]式(1)で表される単位が、-[CF2-CF(O(CF2)3CONH-C3H6-SiR2 m1(W1)3-m1)]-または-[CF2-CF(O(CF2)3CONH-C2H4-NH-C3H6-SiR2 m1(W1)3-m1)]-である、[1]の含フッ素重合体。
(式中、R2は、それぞれ独立に、アルキル基であり、W1は、それぞれ独立に、ハロゲン原子またはアルコキシ基であり、m1は、それぞれ独立に、0、1または2である。)
X1、X2、Q1およびRf1は、請求項1で定義されたとおりであり、
Z2は、ハロゲン原子、OHまたはOR7であり、
R7は、アルキル基である。)
[4]Z1がNR1-Y1であり、かつ、Z2がOR7である、[3]の含フッ素重合体。
[5]さらに、フルオロエチレン由来の単位を含む、[1]~[4]のいずれかの含フッ素重合体。
-[CX3X4-CX5X6]-・・・(3)
(式(3)中、
X3およびX4は、それぞれ独立に、水素原子、フッ素原子または塩素原子であり、
X5は、水素原子、フッ素原子または塩素原子であり、
X6は、水素原子、フルオロアルキル基、炭素-炭素原子間にエーテル性酸素原子を有する炭素数2以上のフルオロアルキル基、フルオロアルコキシ基、炭素-炭素原子間にエーテル性酸素原子を有する炭素数2以上のフルオロアルコキシ基、フルオロアルケニル基、または炭素-炭素原子間にエーテル性酸素原子を有する炭素数3以上のフルオロアルケニル基である。)
[7]-COZ1で表される基の含有量が0.01~4mmol/gである、[1]~[6]のいずれかの含フッ素重合体。
X1、X2、Q1およびRf1は、請求項1で定義されたとおりであり、
Z2は、請求項3で定義されたとおりである。)
[9]前記[1]~[7]のいずれかの含フッ素重合体および含フッ素溶媒を含むことを特徴とするコーティング組成物。
[10]前記[1]~[7]のいずれかの含フッ素重合体の硬化物。
[11]前記[10]の硬化物からなる成形体。
[12]成形体がフィルムである、[11]の成形体。
[13]基材と、該基材の表面に設けられた、[1]~[7]のいずれかの含フッ素重合体の硬化物の層とを有することを特徴とする物品。
[14]前記基材表面と前記含フッ素重合体の硬化物の層との間にプライマ層を有する、[13]の物品。
単量体に由来する単位をその単量体名に「単位」を付して表す場合がある。たとえば、フルオロエチレンに由来する単位を「フルオロエチレン単位」と記す。
本明細書における以下の用語の意味は、以下の通りである。
「フルオロエチレン」とは、テトラフルオロエチレン(CF2=CF2)、およびテトラフルオロエチレンの1~3個のフッ素原子が水素原子またはフッ素以外のハロゲン原子(塩素原子、臭素原子またはヨウ素原子)に置換された化合物を意味する。なお、以下、テトラフルオロエチレンを「TFE」、トリフルオロエチレンを「TrFE」、クロロトリフルオロエチレンを「CTFE」とも記す。
本発明の含フッ素重合体は、単位(1)を含む。
X1およびX2は、それぞれ独立に、水素原子またはフッ素原子であり、
Q1は、単結合またはエーテル性酸素原子であり、
Rf1は、フルオロアルキレン基、または炭素-炭素原子間にエーテル性酸素原子を有する炭素数2以上のフルオロアルキレン基であり、
Z1は、NR1-Y1、O-Y2またはS-Y3であり、
R1は、水素原子、アルキル基またはアリール基であり、
Y1、Y2およびY3は、それぞれ独立に、1以上の加水分解性シリル基を有する基である。
Q1は、エーテル性酸素原子が好ましい。
Rf1がフルオロアルキレン基である場合、その炭素数は1~6が好ましく、1~4が特に好ましい。その炭素数が3以上の場合には、熱安定性に優れる点から直鎖構造が好ましい。フルオロアルキレン基としては、熱安定性に優れる点からペルフルオロアルキレン基が好ましい。すなわち、Rf1としては、炭素数1~6のペルフルオロアルキレン基が好ましく、炭素数1~4のペルフルオロアルキレン基が特に好ましい。
Rf1が、炭素-炭素原子間にエーテル性酸素原子を有する炭素数2以上のフルオロアルキレン基である場合、その炭素数は2~10が好ましく、2~6が特に好ましい。炭素数が3以上の場合には、熱安定性に優れる点から直鎖構造が好ましい。フルオロアルキレン基としては、熱安定性に優れる点からペルフルオロアルキレン基が好ましい。すなわち、Rf1としては、炭素-炭素原子間にエーテル性酸素原子を有する炭素数2~10のフルオロアルキレン基が好ましく、炭素-炭素原子間にエーテル性酸素原子を有する炭素数2~6のフルオロアルキレン基が特に好ましい。
加水分解性シリル基は、-SiCH3(OCH3)2および-SiCH3(OC2H5)2がより好ましく、低温硬化性と保存安定性に優れる点から-SiCH3(OCH3)2が特に好ましい。Z1中の加水分解性シリル基の数は、特に限定されないが、1が好ましい。
R3-SiR2 m1(W1)3-m1 (10a)
式(10a)中、
R3は、アルキレン基、アリーレン基、または炭素-炭素原子間にアミノ基を有する炭素数2以上のアルキレン基であり、
R2、W1およびm1は、Z1で定義されたとおりであり好ましい範囲も同様である。
R3が炭素-炭素原子間にアミノ基を有する炭素数2以上のアルキレン基である場合、その炭素数は、2~12が好ましく、4~6が特に好ましい。R3中に含まれるアミノ基は、-NR4-で表され、ここで、R4は、R1と同義であり好ましい範囲も同様である。
R3は、含フッ素溶媒への溶解性に優れる点から、炭素数1~6のアルキレン基、炭素数6~20のアリーレン基および炭素-炭素原子間にアミノ基を有する炭素数2~12のアルキレン基から適宜選択することが好ましく、-C2H4-、-C3H6-、フェニレン基、炭素-炭素原子間に-NH-を有する炭素数4または5のアルキレン基が特に好ましい。
よって、Y1は、C2H4-SiR2 m1(W1)3-m1、C3H6-SiR2 m1(W1)3-m1およびC2H4-NH-C3H6-R2 m1(W1)3-m1が好ましく、C3H6-SiCH3(OCH3)2、C2H4-NR4-C3H6-Si(OC2H5)3およびC2H4-NR4-C3H6-SiCH3(OCH3)2が特に好ましい。
R5-SiR2 m1(W1)3-m1 (10b)
式(10b)中、
R5は、アルキレン基、炭素-炭素原子間にエーテル性酸素原子を有する炭素数2以上のアルキレン基、炭素-炭素原子間にエーテル性酸素原子を有しかつ1以上の水素原子が水酸基に置換されている炭素数2以上のアルキレン基、アリーレン基であり、
R2、W1およびm1は、Z1で定義されたとおりであり好ましい範囲も同様である。
R5としては、合成が容易な点から、炭素-炭素原子間にエーテル性酸素原子を有しかつ1以上の水素原子が水酸基に置換されている炭素数2以上のアルキレン基が好ましく、CH2CH(OH)CH2OC3H6が特に好ましい。
-NHC3H6Si(OCH3)3
-NHC3H6Si(OC2H5)3
-NHC3H6SiCH3(OCH3)2
-NHC3H6SiCH3(OC2H5)2
-NHC2H4NHC3H6Si(OCH3)3
-NHC2H4NHC3H6Si(OC2H5)3
-NHC2H4NHC3H6SiCH3(OCH3)2
-NHC2H4SiCH3(OC2H5)2
-N(C6H5)C3H6Si(OCH3)3
-N(C6H5)C3H6Si(OC2H5)3
-N(C6H5)C3H6SiCH3(OCH3)2
-N(C6H5)C3H6SiCH3(OC2H5)2
-NHC6H4Si(OCH3)3
-NHC6H4Si(OC2H5)3
-NHC6H4SiCH3(OCH3)2
-NHC6H4SiCH3(OC2H5)2
-OCH2CH(OH)CH2OC3H6Si(OCH3)3
-OCH2CH(OH)CH2OC3H6Si(OC2H5)3
-OCH2CH(OH)CH2OC3H6SiCH3(OCH3)2
-OCH2CH(OH)CH2OC3H6SiCH3(OC2H5)2
-SC3H6Si(OCH3)3
-SC3H6Si(OC2H5)3
-SC3H6SiCH3(OCH3)2
-SC3H6SiCH3(OC2H5)2
-[CF2-CF(O(CF2)2-COZ1)]-
-[CF2-CF(O(CF2)3-COZ1)]-
-[CF2-CF(O(CF2)4-COZ1)]-
-[CF2-CF(OCF2CF(CF3)O(CF2)2-COZ1)]-
-[CF2-CF(OCF2CF(CF3)O(CF2)3-COZ1)]-
-[CF2-CF(O(CF2)3O(CF2)2-COZ1)]-
-[CF2-CF(O(CF2)2O(CF2)2-COZ1)]-
-[CH2-CF(CF2OCF(CF3)-COZ1)]-
-[CH2-CF(CF2OCF(CF3)CF2OCF(CF3)-COZ1)]-
熱安定性に優れかつ入手容易な点から、単位(1)としては-[CF2-CF(O(CF2)3-COZ1)]-が好ましく、そのうちでも-[CF2-CF(O(CF2)3CONH-C3H6-SiR2 m1(W1)3-m1)]-および-[CF2-CF(O(CF2)3CONH-C2H4-NH-C3H6-SiR2 m1(W1)3-m1)]-が特に好ましい。含フッ素重合体は、Z1が異なる2種以上の単位(1)を含んでいてもよい。
本発明の含フッ素重合体は、UV硬化が可能な点からは、単位(1a)を含むのが好ましい。その場合、熱硬化とUV硬化との併用が可能な点からは、単位(1)中のZ1がNR1-Y1であり、Z2がOR7であることが特に好ましい。また、各種基材への接着性を高める点からは、単位(1b)を含むことが好ましい。
他の単位は、それぞれ単独または2種以上を組合せて用いることができる。たとえば、含フッ素重合体は、単独の単位(1b)と2種以上の単位(2)を含んでいてもよい。
X1、X2、Q1およびRf1は、式(1)で定義されたとおりであり、
Z2は、ハロゲン原子、OHまたはOR7であり、
R7は、アルキル基である。
CX1X2=CF-Q1-Rf1-COZ2・・・(11)
式(11)中、X1、X2、Q1およびRf1は、式(1)で定義されたとおりであり、Z2は、式(1a)で定義されたとおりである。
Z3は、NR8HまたはNR9-NR10Hであり、
R8およびR9は、それぞれ独立に、水素原子またはアルキル基であり、
R10は、水素原子またはメチル基であり、
X1、X2、Q1およびRf1は、式(1)で定義されたとおりである。
HNR8-H (12)
HNR9-NR10H (13)
-[CX3X4-CX5X6]-・・・(3)
式(3)中、
X3およびX4は、それぞれ独立に、水素原子、フッ素原子または塩素原子であり、
X5は、水素原子、フッ素原子または塩素原子であり、
X6は、水素原子、フルオロアルキル基、炭素-炭素原子間にエーテル性酸素原子を有する炭素数2以上のフルオロアルキル基、フルオロアルコキシ基、炭素-炭素原子間にエーテル性酸素原子を有する炭素数2以上のフルオロアルコキシ基、フルオロアルケニル基、または炭素-炭素原子間にエーテル性酸素原子を有する炭素数3以上のフルオロアルケニル基である。
X6が炭素-炭素原子間にエーテル性酸素原子を有する基である炭素数2以上のフルオロアルキル基の場合、その炭素数は、2~15が好ましく、2~6が特に好ましい。熱安定性に優れる点から、炭素-炭素原子間にエーテル性酸素原子を有する炭素数2以上のペルフルオロアルキル基が好ましく、炭素-炭素原子間にエーテル性酸素原子を有する炭素数2~6のペルフルオロアルキル基が特に好ましい。
X6が炭素-炭素原子間にエーテル性酸素原子を有する炭素数2以上のフルオロアルコキシ基である場合、その炭素数は、2~15が好ましく、2~6が特に好ましい。熱安定性に優れる点から、炭素-炭素原子間にエーテル性酸素原子を有する炭素数2以上のペルフルオロアルコキシ基が好ましく、炭素-炭素原子間にエーテル性酸素原子を有する炭素数2~6のペルフルオロアルコキシ基が特に好ましい。エーテル性酸素原子を有するフルオロアルコキシ基としては、-OCF2CF(CF3)O(CF2)2CF3が最も好ましい。
Y2が炭素-炭素原子間にエーテル性酸素原子を有する炭素数3以上のフルオロアルケニル基である場合、その炭素数は、3~16が好ましく、3~7が特に好ましい。熱安定性に優れる点から、炭素-炭素原子間にエーテル性酸素原子を有する炭素数3以上のペルフルオロアルケニル基が好ましく、炭素-炭素原子間にエーテル性酸素原子を有する炭素数3~7のペルフルオロアルケニル基が特に好ましい。
-[CH2-CH2]-、-[CF2-CF(CF3)]-、-[CH2-CF(CF3)]-、-[CF2-CF(OCF3)]-、-[CF2-CF(OCF2CF3)]-、-[CF2-CF(O(CF2)2CF3)]-、-[CF2-CF(O(CF2)3CF3)]-、-[CF2-CF(OCF2CF(CF3)O(CF2)2CF3)]-、-[CF2-CF(O(CF2)4OCF=CF2)]-、-[CF2-CF((CF2)4CF=CF2)]-、-[CF2-CF((CF2)5CF=CF2)]-、-[CF2-CF((CF2)6CF=CF2)]-。
CX3X4=CX5X6・・・(31)
式(31)中、X3、X4、X5およびX6は、式(3)で定義されたとおりである。
なお、X6が前記フルオロアルケニル基である場合、化合物(31)におけるフルオロアルケニル基中の二重結合は重合に関与せず、化合物(31)の重合によりフルオロアルケニル基を有する単位(3)が形成される。
含フッ素重合体中の各単位の含有量は、19F-NMR、1H-NMR測定により算出できる。
本発明の含フッ素重合体は、単位(1a)を含みかつ前記単位(1)を含まない含フッ素重合体(以下、単に「前駆体」とも記す。)と、アミノシラン化合物、エポキシシラン化合物、メルカプトシラン化合物およびイソシアナトシラン化合物からなる群より選択される少なくとも1種のシラン化合物と反応させることによって製造することができる。これらのシラン化合物は、それぞれ単独または2種以上を組合せて用いることができる。
前駆体は、公知の方法(たとえば国際公開第2015/098773号に記載の方法)で重合させることにより得られる。
HNR1-Y1 (5)
式(5)中、R1およびY1は、式(1)で定義されたとおりであり好ましい範囲も同様である。
アミノシラン化合物としては、N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルメチルジエトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリエトキシシラン、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-アミノプロピルメチルジメトキシシラン、3-アミノプロピルメチルジエトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシラン、N-フェニル-3-アミノプロピルトリエトキシシラン、N-フェニル-3-アミノプロピルメチルジメトキシシラン、N-フェニル-3-アミノプロピルメチルジエトキシシランが特に好ましい。
Ep-Y21 (6)
式(6)中、Epは、エポキシ基(すなわち、1,2-エポキシエチル基)であり、Y21は、Y2と同義であり、R6-SiR2 m1(W1)3-m1が好ましい。
エポキシシラン化合物としては、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリエトキシシランが特に好ましい。
HS-Y3 (7)
式(7)中、Y3は、式(1)で定義されたとおりであり好ましい範囲も同様である。
メルカプトシラン化合物としては、3-メルカプトプロピルメチルジメトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-メルカプトプロピルメチルジエトキシシラン、3-メルカプトプロピルトリエトキシシランが特に好ましい。
O=C=N-Y4 (8)
式(8)中、Y4は、Y3と同義であり好ましい範囲も同様である。
イソシアナトシラン化合物としては、3-イソシアナトプロピルメチルジメトキシシラン、3-イソシアナトプロピルトリメトキシシラン、3-イソシアナトプロピルメチルジエトキシシラン、3-イソシアナトプロピルトリエトキシシランが好ましい。
(a)Z2がOR7である単位(1a)を含む前駆体と、アミノシラン化合物とを反応させる
(b)Z2がハロゲン原子である単位(1a)を含む前駆体と、アミノシラン化合物またはイソシアナトシラン化合物とを反応させる
(c)Z2がOHである単位(1a)を含む前駆体と、イソシアナトシラン化合物とを反応させる
(d)Z2がOHである単位(1a)を含む前駆体と、エポキシシラン化合物とを反応させる
(e)Z2がハロゲン原子である単位(1a)を含む前駆体と、エポキシシラン化合物とを反応させる
(f)Z2がハロゲン原子である単位(1a)を含む前駆体と、メルカプトシラン化合物とを反応させる
フッ素化アルカンとしては、炭素数4~8の化合物が好ましい。市販品としては、たとえばC6F13H(旭硝子社製、アサヒクリン(登録商標)AC-2000)、C6F13C2H5(旭硝子社製、アサヒクリン(登録商標)AC-6000)、C2F5CHFCHFCF3(ケマーズ社製、バートレル(登録商標)XF)等が挙げられる。
フッ素化芳香族化合物としては、たとえばヘキサフルオロベンゼン、トリフルオロメチルベンゼン、ペルフルオロトルエン、ビス(トリフルオロメチル)ベンゼン等が挙げられる。
フルオロアルキルエーテルとしては、炭素数4~12の化合物が好ましい。市販品としては、たとえばCF3CH2OCF2CF2H(旭硝子社製、アサヒクリン(登録商標)AE-3000)、C4F9OCH3(3M社製、ノベック(登録商標)7100)、C4F9OC2H5(3M社製、ノベック(登録商標)7200)、C2F5CF(OCH3)C3F7(3M社製、ノベック(登録商標)7300)等が挙げられる。
フッ素化アルキルアミンとしては、たとえばペルフルオロトリプロピルアミン、ペルフルオロトリブチルアミン等が挙げられる。
フルオロアルコールとしては、たとえば2,2,3,3-テトラフルオロプロパノール、2,2,2-トリフルオロエタノール、ヘキサフルオロイソプロパノール等が挙げられる。
本発明の含フッ素重合体は、水分により加水分解・縮合反応して架橋し、硬化物が得られる。したがって、本発明の含フッ素重合体を成形するとともに水分により硬化させて成形体を製造することができる。一方、本発明の含フッ素重合体は、通常、粘度の高い液状物であり、成形は液体を使用した成形が必要となる。よって、担体上に含フッ素重合体の膜を形成し、その膜の表面を水分に接触させるとともに膜内部まで水分を浸透させて硬化させることにより、硬化物を製造することが好ましい。硬化物を担体から剥離することにより、硬化物からなる成形体を得ることができる。一方、担体として、非剥離性の担体を使用し、担体上に硬化物が一体化した成形体を得ることもできる。以下、非剥離性の担体を「基材」という。
含フッ素重合体の硬化のために水分が必要であり、水分の供給は、通常、含フッ素重合体の膜に水分を含む空気を接触させることによって行われる。水分の供給は、水分を含む空気以外の気体と接触させる方法や含水液体に接触させることによっても行うことができる。
前記剥離性担体としては、フッ素樹脂等の非付着性材料からなる担体、表面処理等により剥離性表面とした、樹脂や金属等の各種材料からなる担体が挙げられる。特に、少なくとも表面が非付着性含フッ素材料からなる担体が好ましい。
基材の表面は、プライマ層を有していてもよい。プライマ層を形成するプライマは、基材と後述するコーティング組成物中の溶媒との組み合わせにより適宜選定される。たとえば、シランカップリング剤やエポキシ系エラストマが挙げられる。プライマ層は、基材表面と硬化物層の密着力が不充分となるおそれのある基材に対して設けられることが好ましいそのような基材としては、たとえば樹脂表面を有する基材が挙げられる。
また、樹脂表面を有する基材の場合は、樹脂の表面は、UV処理、コロナ処理、プラズマ処理等で処理されていてもよい。これらの処理をした樹脂の表面にプライマ層を有していてもよい。
基材と一体化された硬化物においては、硬化物の厚さは前記フィルムの厚さよりもより薄いものとすることができる。なお、以下、基材と一体化された硬化物を、基材上の「層」という。層の厚さは、0.1~300μmが好ましく、1~200μmがより好ましく、10~150μmが特に好ましい。上記厚さの上限以下では、含フッ素重合体が充分に硬化し、基材と一体化された硬化物が得られる。下限以上では硬化物の強度が確保されるとともに基材を保護する機能が発揮される。
コーティング組成物を剥離性担体や基材に塗布し、溶媒を除去することにより含フッ素重合体の膜を形成することができる。この際、含フッ素重合体よりも低粘度の液体を用いて該液体の膜を形成することができるので、塗布操作が容易であり、また、含フッ素重合体の膜の厚さの調整も容易である。さらに、目的に応じて種々の添加剤を配合することも容易である。
以下、基材上に本発明の含フッ素重合体の硬化物からなる層を形成する場合を例として、上記コーティング組成物とその使用方法等を説明する。なお、上記のように、下記コーティング組成物とその使用方法により、フィルムやその他の成形物を製造することができることは言うまでもない。
本発明におけるコーティング組成物は、本発明の含フッ素重合体と溶媒とを含む。含フッ素重合体を製造した際の含フッ素重合体および含フッ素溶媒を含む反応生成物をそのまま用いてもよい。コーティング組成物中の含フッ素重合体の含有量は、1~99質量%が好ましく、1~50質量%がより好ましく、5~30質量%が特に好ましい。前記範囲であると、含フッ素重合体の硬化物の厚さを調整できる。
前記有機酸としては、メタンスルホン酸、ベンゼンスルホン酸、p-トルエンスルホン酸、シュウ酸、トリクロロ酢酸、トリフルオロ酢酸、ペンタフルオロ安息香酸、ヘキサフロログルタール酸、オクタフロロアジピン酸等が好ましく、少量で縮合を促進できる点で、p-トルエンスルホン酸が特に好ましい。
コーティング組成物中の硬化触媒の含有量は、含フッ素重合体に対して0.01~1質量%が好ましく、0.05~0.2質量%が特に好ましい。前記範囲であると、硬化速度に優れかつコーティング組成物の保存安定性に優れる。
本発明の含フッ素重合体は加水分解性シリル基を有するため、空気中の水分により低温で架橋する。架橋は溶媒除去の過程や溶媒除去後の加熱で生じる。溶媒除去および溶媒除去後の加熱は低温で行うことが好ましい。低温とは、室温(たとえば、20℃)から150℃の範囲であることを意味し、室温から100℃未満であることが好ましく、室温から90℃の範囲であることが特に好ましい。
基材の材質が金属やセラミックの場合は、溶媒の残留による発泡や密着性の不良等の不具合を避けるために、溶媒の沸点以上の温度まで加熱することが好ましい。一方、基材の材質が樹脂の場合には加熱による基材の変形を抑えるために、樹脂の変形温度以下の沸点の溶媒を用いて、変形温度以下で溶媒を揮発させることが好ましい。
(質量平均分子量)
含フッ素重合体および前駆体の質量平均分子量は、CF2ClCF2CHClF(旭硝子社製、商品名:AK-225cb)を溶媒として用いて、ゲルパーミエーションクロマトグラフィ(GPC)によりPMMA(ポリメチルメタクリレート)換算分子量として算出した。
(各基の含有量)
含フッ素重合体中および前駆体中の、-COZ1で表される基、-COOCH3および-COCF=CF2の含有量は、19F-NMRから求めた。
(弾性率およびTg)
各例で製造したフィルムを用い、日立ハイテク社製TMA/EXSTAR SS7100の粘弾性解析モードにより測定した。測定温度範囲:-50℃~200℃、昇温速度:5℃/分、周波数:0.05Hz。
(外観)
得られたフィルムの外観を観察し、以下の基準で評価した。
○(良好):ムラも発泡も確認できなかった
△(可):ムラが見えた
×(不良):発泡が生じた
(浸漬試験)
得られたフィルムをAC-2000中に浸漬した。フィルムの形状変化を確認し、以下の基準で評価した。
○(良好):わずかに膨潤するのみでフィルムの形状は保持されていた
△(可):フィルムの形状が変形した
×(不良):溶解して形状は維持されなかった。
(耐熱試験)
得られたフィルムを熱風オーブン中、200℃で30分間加熱した。フィルムの発泡の有無を確認し、以下の基準で評価した。
○(良好):発泡が生じなかった
×(不良):発泡が生じた
(破断伸度および破断強度)
得られたフィルムの200℃における破断伸度および破断強度を、日立ハイテク社製TMA/EXSTAR SS7100の変位制御モードにより測定した。引張速度:1mm/分。
スライドガラス2枚を含フッ素重合体で接着面が2.5cm×0.5cmとなるように張り合わせ、60℃の乾燥器中で加熱した。次いで、60℃の水または50℃のアセトンに浸漬し、24時間保持した。スライドガラスの剥がれの有無を確認し、以下の基準で評価した。
○(良好):剥がれなし
×(不良):剥がれあり
(耐薬品性)
アクリル樹脂シート(3cm×1cm、厚さ1mm)を、コーティング組成物(固形分濃度15質量%)中に浸漬し引き上げたのち室温で1時間乾燥した。再度、コーティング組成物中に浸漬し引き上げた。室温で1時間乾燥したのち、60℃乾燥機中でさらに1時間乾燥して、含フッ素重合体の硬化物の層を備えたアクリル樹脂シートを得た。含フッ素重合体の硬化物の厚さは質量変化から計算して約10μmであった。これをアセトン中に室温で5時間浸漬して、アクリル樹脂シートの溶解の有無を確認し、以下の基準で評価した。
○(良好):溶解なし
×(不良):溶解あり
内容積が1Lの撹拌機付きステンレス製オートクレーブに、重合開始剤としてV601(和光純薬社製)の0.5gを仕込み減圧脱気した後、CF2=CFOCF2CF2CF2COOCH3の48g、CF2=CFOCF2CF2CF3(以下、「PPVE」とも記す。)の795g、AC-2000の36gを仕込んだ。撹拌しながらTFEの122gを圧入した後、内温を70℃まで昇温して4時間重合を行った。この間に圧力が1.26MPaから0.94MPaまで低下したことから反応の進行を確認した。
前駆体P1の1.2gをAC-2000の8.8gに溶解した後、3-アミノプロピルメチルジメトキシシラン(東京化成社製)を脱水メタノールで5倍に希釈した溶液の0.25gを添加して室温で激しく撹拌し、含フッ素重合体P21を含む反応生成物を得た。反応生成物の一部(1.2g)をコーティング組成物とした。コーティング組成物中の含フッ素重合体P21の含有量は12.0質量%であり、コーティング組成物中の溶媒の含有量は87.8質量%であり、溶媒中の含フッ素溶媒の含有量は97.8質量%であった。
コーティング組成物をETFEシート(旭硝子社製アフレックス)で作成した箱型ボート(縦2cm、横2cm、深さ7mm)に流し込みホットプレート上で40℃、1時間、次いで60℃、1時間加熱により溶媒を揮発させて、厚さが160μmの無色透明なフィルムを作成した。
評価結果を表1~2に示す。
例1で得た前駆体P1の1.2gをAC-2000の6.8gに溶解した後、N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン(東京化成社製)を脱水メタノールで5倍に希釈した溶液の0.12gを添加して室温で激しく撹拌し、含フッ素重合体P22を含む反応生成物を得た。反応生成物の一部(1.2g)をコーティング組成物とした。コーティング組成物中の含フッ素重合体P22の含有量は15.1質量%であり、コーティング組成物中の溶媒の含有量は84.8質量%であり、溶媒中の含フッ素溶媒の含有量は98.6質量%であった。
コーティング組成物を例1同様の箱型ボートに流し込みホットプレート上で30℃、50℃、70℃で各1時間ずつ加熱により溶媒を揮発させて、厚さが230μmのフィルムを作成した。
評価結果を表1~2に示す。
例1で得た前駆体P1の1.2gをAC-2000の6.8gに溶解した後、アミノプロピルトリエトキシシラン(東京化成社製)の0.05gを添加して溶液が均一になるまで室温で激しく撹拌し、含フッ素重合体P23を含む反応生成物を得た。反応生成物の一部(1.2g)をコーティング組成物とした。コーティング組成物中の含フッ素重合体P23の含有量は15.2質量%であり、コーティング組成物中の溶媒の含有量は84.5質量%であり、溶媒中の含フッ素溶媒の含有量は100質量%であった。
コーティング組成物を例1同様の箱型ボートに流し込みホットプレート上で30℃、50℃、70℃で各1時間ずつ加熱により溶媒を揮発させて、厚さが200μmのフィルムを作成した。
評価結果を表1~2に示す。
AC-2000の替わりにノベック7300(C2F5CF(OCH3)C3F7)を用いた以外は例1と同様にして、含フッ素重合体P24を含む反応生成物を得た。反応生成物の一部(1.2g)をコーティング組成物とした。コーティング組成物中の含フッ素重合体P24の含有量は12.0質量%であり、コーティング組成物中の溶媒の含有量は87.8質量%であり、溶媒中の含フッ素溶媒の含有量は97.8質量%であった。
コーティング組成物を例1同様の箱型ボートに流し込みホットプレート上で40℃、1時間、60℃、1時間、次いで90℃、30分加熱により溶媒を揮発させたところ、白濁部分と透明部分のまだらなフィルムが得られた。
評価結果を表1~2に示す。
国際公開第2009/096342号の合成例1に基づいて、単位(2-1)と、CF2=CFOC4F8OCF=CF2(以下、「C4DVE」とも記す。)単位(3-2)と、PPVE単位(3-1)とが67:7:26(モル比)である含フッ素重合体Xを製造した。次に、含フッ素重合体Xの0.3gにAC-2000の1.7gを添加し、コーティング組成物を得た。コーティング組成物中の含フッ素重合体Xの含有量は15質量%であり、コーティング組成物中の溶媒の含有量は85質量%であり、溶媒中の含フッ素溶媒の含有量は100質量%であった。
コーティング組成物の0.8gを例1同様の箱型ボードに流し込み、40℃、1時間、60℃、1時間、次いで90℃、30分、150℃、30分間加熱して厚さ100μmの無色透明のフィルムを得た。一方、前記と同様に製造したコーティング組成物の1.6gを例1同様の箱型ボードに流し込み、40℃、1時間、60℃、1時間、次いで90℃、30分、150℃、30分間加熱して厚さ200μmのフィルムを得ようとしたが、発泡して外観不良であった。また、コーティング組成物の0.8gを例1同様の箱型ボードに流し込み、例1と同様ホットプレート上で40℃で1時間、次いで60℃で1時間加熱しても含フッ素重合体が熱架橋せずフィルムが得られなかった。
評価結果を表1~2に示す。
例5は、60℃での低温ではフィルムを形成することができず、低温硬化が可能ではなかった。また、150℃での加熱によって熱硬化した場合であっても、厚さが200μmのフィルムでは硬化時点で発泡が確認された。
エポフレンド(ダイセル社製、エポキシ化熱可塑性エラストマ)の1部をシクロペンタノンの100部に溶解してプライマ溶液を作成した。硬質塩化ビニル樹脂シート(サイズ3cm×5cm、厚さ1mm)の片面にプライマ溶液を塗布して室温で1日乾燥し、厚さ10μmのプライマ層を形成した。次に、プライマ層の上に例2で得たコーティング組成物を塗布して室温で1時間、50℃で1時間、70℃で5分加熱乾燥し、厚さ60μmの含フッ素重合体P22の硬化物の層を形成した。
上記硬化物層に対して碁盤目カットテープ剥離を行った結果、100か所中、1か所も剥離せずに残っており、本発明の含フッ素重合体の硬化物は硬質塩化ビニル樹脂に対してプライマを介して接着可能であった。このように適切なプライマと溶媒との組み合わせを選択することにより、本発明の含フッ素重合体は耐熱温度が限定される樹脂製基材に対して硬化接着させることが可能である。
サイズ2cm×5cm、厚さ2mmのニッケル製テストピースの片面に例2のコーティング組成物を塗布して室温で1時間、50℃で1時間、次いで100℃で30分間乾燥し、厚さ50μmの含フッ素重合体P22の硬化物の層を形成した。
上記硬化物層に対して碁盤目カットテープ剥離を行った結果、1か所も剥離せずに残っており、プライマなしでも直接接着した。このように本発明の含フッ素重合体は金属製基材に対して直接硬化接着することが可能である。
例2のコーティング組成物のかわりに例5のコーティング組成物を用いた以外は例7と同様にニッケル製テストピース上に厚さ50μmの含フッ素重合体Xの層を形成し、次いで、低圧水銀ランプの紫外光を照射して該含フッ素重合体Xを硬化させた。
硬化した含フッ素重合体Xの層に対し碁盤目テープ剥離を行ったところ、100か所中、10か所しか被膜が残らなかった。したがって、公知例の例5の含フッ素重合体はニッケルへの接着性は乏しかった。
本発明の含フッ素重合体は、光学材料、素子用封止材、無機EL蛍光体分散材、光導波路用材料、耐熱・耐薬品性のシーリング材、接着剤、コーティング材として有用である。本発明のコーティング組成物は、離型剤、防汚コート用材料、耐薬品保護コート用材料等に有用である。
本発明の含フッ素重合体から形成される硬化物からなる成形品は、光ファイバのクラッド材料、光導波路のコア材料やクラッド材料として有用である。
本発明の含フッ素重合体から形成される硬化物を備える基材は、発光素子、半導体素子、太陽電池素子、短波長光発光素子、電線およびそれを用いたコイル等として有用である。
なお、2016年08月29日に出願された日本特許出願2016-167131号の明細書、特許請求の範囲、要約書および図面の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (14)
- 式(1)で表される単位が、-[CF2-CF(O(CF2)3CONH-C3H6-SiR2 m1(W1)3-m1)]-または-[CF2-CF(O(CF2)3CONH-C2H4-NH-C3H6-SiR2 m1(W1)3-m1)]-である、請求項1に記載の含フッ素重合体。
(式中、R2は、それぞれ独立に、アルキル基であり、W1は、それぞれ独立に、ハロゲン原子またはアルコキシ基であり、m1は、それぞれ独立に、0、1または2である。) - Z1がNR1-Y1であり、かつ、Z2がOR7である、請求項3に記載の含フッ素重合体。
- さらに、フルオロエチレン由来の単位を含む、請求項1~4のいずれか一項に記載の含フッ素重合体。
- さらに、下式(3)で表される単位(ただし、フルオロエチレン由来の単位を除く。)を含む、請求項1~5のいずれか一項に記載の含フッ素重合体。
-[CX3X4-CX5X6]-・・・(3)
(式(3)中、
X3およびX4は、それぞれ独立に、水素原子、フッ素原子または塩素原子であり、
X5は、水素原子、フッ素原子または塩素原子であり、
X6は、水素原子、フルオロアルキル基、炭素-炭素原子間にエーテル性酸素原子を有する炭素数2以上のフルオロアルキル基、フルオロアルコキシ基、炭素-炭素原子間にエーテル性酸素原子を有する炭素数2以上のフルオロアルコキシ基、フルオロアルケニル基、または炭素-炭素原子間にエーテル性酸素原子を有する炭素数3以上のフルオロアルケニル基である。) - -COZ1で表される基の含有量が0.01~4mmol/gである、請求項1~6のいずれか一項に記載の含フッ素重合体。
- 請求項1~7のいずれか一項に記載の含フッ素重合体および含フッ素溶媒を含むことを特徴とするコーティング組成物。
- 請求項1~7のいずれか一項に記載の含フッ素重合体の硬化物。
- 請求項10に記載の硬化物からなる成形体。
- 成形体がフィルムである、請求項11に記載の成形体。
- 基材と、該基材の表面に設けられた、請求項1~7のいずれか一項に記載の含フッ素重合体の硬化物の層とを有することを特徴とする物品。
- 前記基材表面と前記含フッ素重合体の硬化物の層との間にプライマ層を有する、請求項13に記載の物品。
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KR20210097737A (ko) | 2018-11-26 | 2021-08-09 | 샌트랄 글래스 컴퍼니 리미티드 | 감광성 수지 조성물, 함불소 수지 경화물의 제조 방법, 함불소 수지, 함불소 수지막, 뱅크 및 표시 소자 |
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